This invention relates to an apparatus for continuously producing a polyacetylene film by Ziegler-Natta catalyst.
A polyacetylene is the most simple chain conjugated high-molecular compound which contains as ingredients a carbon atom and a hydrogen atom, and has properties as a semiconductor. Particularly, a polyacetylene membrane which is laminated with Ziegler-Natta catalyst (Ti(OC--H--)--Al(C--H--) series) has fibril (fibrous ultrafine crystal) mesh structure of approx. 200 A in diameter. When this membrane slightly doped with halogen gas or arsenic pentafluoride, its conductivity can be largely varied.
Since such a polyacetylene membrane has extremely chemical stability, a light weight and a fibril mesh structure, resulting in a large surface area, the polyacetylene membrane has already noted as favorable electrode materials for a secondary battery or applications for integrated circuits.
In order to produce the above-described polyacetylene film, it was heretofore known to produce the polyacetylene film by the method which has the steps of preparing the molar ratio of aluminum/titanium of the Ziegler-Natta catalyst to 4 to 4, and cooling the catalyst at -78.degree. C. with a refrigerant of a dry ice methanol, blowing acetylene gas to the catalyst, thereby polymerizing the gas in the vicinity of the boundary between the vapor phase and the liquid phase in the surface of the catalyst solution.
When the polyacetylene film is heretofore actually produced, a substrate b made, for example, of glass is contained, as shown in FIG. 1, in a vessel a, the Ziegler-Natta catalyst is coated on the surface of the substrate b, acetylene gas introduced via a supply tube c into the vessel a is blowed to the substrate b, thereby polymerizing to produce the polyacetylene film d of the same shape as the substrate b. Reference character e in FIG. 1 designates an acetylene gas exhaust tube.
In the conventional case, the substrate b must be, however, exchanged whenever the film is produced in a troublesome manner, and the polyacetylene film thus produced is limited in thickness and area, resulting in a difficulty in the low productivity.
In order to improve the productivity of the polyacetylene film, it is considered to, for example, store Ziegler-Natta catalyst in a coverless vessel, polymerize acetylene gas in the vicinity of the boundary between the vapor phase and the liquid phase in the surface of the catalyst, and thus continuously draw the polyacetylene film thus formed. In this case, it is not only difficult to smoothly draw the polyacetylene film, but also excessive catalyst is adhered to the produced polyacetylene film. Accordingly, even if the film is cleaned, the catalyst is not completely removed, and disadvantageously affects the adverse influence to the characteristics of the produced film.